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Terri Christison Senior Marketing Specialist – IC/SP Thermo Fisher Scientific March 6, 2014

Inorganic Anion Analysis of Wastewater Using Discrete Analyzers

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Outline

• Wastewater • Sources • Reasons for analysis • Analytical challenges

• Common anions in wastewater • Anion measurement instrumentation • Discrete analysis

• Automated photometric assays • Accurate, precise measurement

• Conclusion

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Wastewater

• Municipal or household waste • Sewage effluent • Raw sewage • Treated effluent • Leachates • Surface run-off

• Industrial • Production effluents • Process and cooling waters

• Agriculture • Soils - leached/extracted into solution

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Reasons to Perform Wastewater Analysis

• Monitoring discharge • Regulatory limits

• Nutrient Analysis • Excessive plant growth in aqueous environments

• Known samples • Historical analysis

• E.g., High chloride level from a treatment facility with a water inlet near the sea/estuary

• Unknown samples • Investigative, pollution incident, farm run-off, milk spill, or industrial

discharge due to plant failure

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Wastewater Analytical Challenges

• The content of wastewater samples is often unknown • Accurate, rapid results are needed • Samples out of calibration range will have to be rerun

• Ability to automatically perform dilutions pre- or post-run is advantageous

• Samples can contain disparate analyte concentrations • May need to run multiple dilutions depending on the analytes of interest

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Common Anions in Wastewater

• Inorganic anions • Chloride

• Disrupts nitrification process (treatment) • Sulfate

• Disrupts anaerobic digestion process (treatment) • Phosphate, nitrate, nitrite

• Plant nutrients; phytoplankton blooms • Bromide

• Ozonation, chlorination -> Disinfection by products: brominated trihalomethanes, bromate (carcinogens)

• Organic acids • Formic, acetic, propionic acids

• pH balance

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Measurement of Anions in Wastewater

• Ion chromatography (IC) • Sample separated into its constituents • Automated; conductivity detection

• Manual, wet chemical assays • Photometric (spectrometer)

• Continuous flow analysis (CFA) • Segmented flow analysis (SFA); flow injection analysis (FIA); sequential

injection analysis (SIA) • Semi-automated; photometric

• Discrete analysis • Individual tests for specific analytes • Automated; photometric

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Data Management

Conductivity Detector

High-Pressure Non-Metallic Pump

Eluent Generator

(OH– or H+)

Waste

Sample Inject (Autosampler) Recycle

Mode

Detection

DI H20

CR-TC

Cell Effluent

Electrolytic Eluent

Suppressor

Separation Column

Ion Chromatography System

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Anions in Hydraulic Fracturing Flowback Wastewater

Peaks: Measured Undiluted 1. Acetate < 0.05 mg/L < 5 2. Formate < 0.05 < 5 3. Chloride 940.0 94,000 4. Sulfate 0.12 12 5. Bromide 8.90 890

0.0

0.65

µS

Minutes

0 2 4 8

0

2,400

µS

Minutes

3

1 2

3

4

5

6

0 2 4 8 6

5

4

1 2

Column: Thermo Scientific™ Dionex™ IonPac™ AG18/AS18 columns , 4 mm i.d. Eluent Source: Thermo Scientific Dionex EGC III KOH cartridge Eluent: 39 mM KOH Flow Rate: 1 mL/min Inj. Volume: 25 µL Col. Temp.: 30 ° C Detection: Suppressed conductivity, Thermo Scientific™ Dionex™ ASRS™ 300 Anion Self- Regenerating Suppressor, recycle mode Sample: 100-fold fracking flowback, filtered, 0.2 µm

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Fast Determination of Inorganic Anions in Municipal Wastewater

Peaks: A B C D 1. Chloride 76.5 146 154 130 mg/L 2. Nitrite 1.5 2.1 37.4 1.6 3. Carbonate -- -- -- -- 4. Sulfate 41.6 88.9 84.8 91.8 5. Nitrate 28.8 7.2 31.7 128

3

4

4 0 Minutes

3 2 1 0

1.7

µS

B

A

5

2

1

C

D

Column: Dionex IonPac AG18-4µm, Dionex IonPac AS18-4µm, 0.4 mm i.d. Eluent Source: Dionex EGC-KOH Cartridge (Capillary) Eluent: 23 mM KOH Flow Rate: 0.025 mL/min Inj. Volume: 0.4 µL Column Temp.: 30 ° C IC Cube Temp.: 15 ° C Detection: Suppressed conductivity, Thermo Scientific™ Dionex™ ACES™ 300 Anion Capillary Electrolytic Suppressor, recycle mode Sample Prep: Diluted 1000-fold, filtered, 0.2 µm Samples: A: Influent B: Primary effluent C: Trickling effluent D: Final effluent

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A Complete Family of Ion Chromatography Systems

Thermo Scientific

Dionex ICS-900 IC System

Thermo Scientific

Dionex ICS-1100 IC System

Thermo Scientific

Dionex ICS-1600 IC System

Thermo Scientific Dionex ICS-5000+ HPIC System

Thermo Scientific

Dionex ICS-2100 IC System

Thermo Scientific Dionex

ICS-4000 HPIC System

Reagent-Free™ IC (RFIC™)

High-Pressure IC™ (HPIC™)

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Anion Determinations Using Photometric Assays

• Manual wet chemistry assays • Labor intensive • Wastes reagents • Error prone

• Continuous flow analyzers • Relatively slow • Generates a lot of waste

• Discrete analyzers • Rapid, automated, efficient

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Benefits of Automated Discrete Analysis

• Flexible – various tests can be performed on each sample; there is no limitation on number of tests

• Fast – ready for immediate analysis, no reagent priming, no method changeover time

• Precise – specific measurements with high reproducibility, achieves low detection levels

• Minimal carry-over – each reaction takes place in its own reaction cuvette

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Discrete Analysis Process

1. Cuvette entry point 2. Cuvette loader 3. Incubator 4. Sample racks 5. Sample disk 6. Reagents 7. Reagent disk 8. Barcode reader 9. Reagent dispenser 10. Sample dispenser 11. Mixer 12. Photometer unit

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Fast Photometric Measurement

• Spectral range 275 – 880 nm • 12 filter positions

• Fast measurement with a flash lamp • Main and side wavelengths measured at the same time • Water blank measured in all wavelengths at the same time

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Flexible, Reliable, Temperature-Stabilized Measurement

• Several calibration options • Factor, Bias, Linear, Logit-log, Spline, Polynomial, Point-to-point

• Possibility to add up to four reagents per test • Automation even for the most complex methods

• Real-time QC program assures reliable performance

• Measurement temperature can be

adjusted between 25 oC and 60 oC

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Flexible Sample Management

• Sample volumes from 2 to 120 µL

• Any mix of sample containers • 0.5, 2.0 and 4.0 mL sample cups • 5.0, 7.0 or 10.0 mL sample tubes

• Automatic identification via

internal barcode reader

• Tests can be requested individually or using a profile

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Easy Reagent Handling

• Reagent volumes from 2 to 240 µL • Reagent containers

• 10 and 20 mL vials • Barcoded system reagent containers

are automatically identified • Non-system reagents can be entered

without barcodes • Clearly displayed

• Real-time reagent volume • Remaining test capacity • Expired reagents flagged automatically

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Comprehensive Data Handling

• Application parameter values readable from barcode or electronically from a file

• Results • Calculated from both measured

and off-line results • Automatically flagged in case of

• Abnormal values • Repeats • Out-of-limit control values

• Long term storage of results • Associated calibrations • Reagent lot data

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Reporting Options

• Reports available

• Spreadsheet export for further calculations

• Export to LIMS • Printouts • PDF files

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Intuitive User Interface

• Graphical user-interface • Provides fast guidance • Includes context-sensitive help • Available in different languages

• Secure and traceable data handling

• Different user groups can have different access rights

• Touch screen option

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• Chloride • Fluoride • Nitrate - Hydrazine • Nitrate - Enzymatic • Nitrate - Vanadium • Nitrite • Ortho-Phosphate • Sulfate • T.O.N • TKN as N • TP as P

• Additional analytes • Alkalinity • Ammonia • Calcium • Chromium (VI) • Magnesium • Silica • Total Hardness • Urea • pH • Conductivity

Wide Selection of Tests Optimized for Anions

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Chloride: Calibration Curves

• Using Thermo Scientific Chloride R1 reagent

Low Chloride (0–20 mg/L) High Chloride (20–100 mg/L)

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Chloride: Precision and Accuracy

Sample Avg*

Result (mg/L)

Std. Dev. Avg*

% Recovery

Std. Dev. Accuracy

Cl_Low_10 10.01 100.1 100.1 1.52% 1.00 Cl_High_80 83.18 0.56 104.0 0.70% 1.04

*n = 20

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Chloride: Method Detection Limit

Sample Result (mg/L)

% Recovery

Cl_Low_0.5 0.503 101 Cl_Low_0.5 0.514 103 Cl_Low_0.5 0.485 97 Cl_Low_0.5 0.474 95 Cl_Low_0.5 0.482 96 Cl_Low_0.5 0.410 82 Cl_Low_0.5 0.407 81 Avg. 0.468 94 Std. Dev. 0.043 MDL 0.14

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Chloride: Matrix Spiking

Sample Result (mg/L)

% Recovery RPD

Wastewater* 443.0 Wastewater_MS50 489.0 101

Wastewater_MSD50 489.8 103 0.2 Saline water (dil)* 140.4 Saline water (dil)_MS50 187.3 103 Saline water (dil)_MSD50 186.9 102 0.2

50 mg/L chloride spike; Saline water was diluted 100-fold; RPD = relative percent difference * Corrected for volume

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Thermo Scientific System Reagents

• Optimized system solution • System applications for water analysis • Loadable application data from 2D barcode • Optimized kit sizes and on-board stability • Wide range of calibrators

• Productivity and efficiency • Ready-to-use liquid reagents eliminate

reagent preparation • Minimal reagent waste • Bar-coded reagent vials provide easy and

reliable identification • lot, expiration date, vial size • real-time reagent monitoring

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Range of Discrete Analyzers for Wastewater Analysis

Thermo Scientific™ Gallery™/ Thermo Scientific™ Aquakem™ 200

Aquakem 250 Gallery Plus Aquakem 600

Capacity (tests/hr)

Up to 200 Up to 250 Up to 350 Up to 600

Incubation temperature

25 to 60 ˚C (Gallery) 37 ˚C (Aquakem) 37 ˚C 25 to 60 ˚C 37 ˚C

Optional units

pH and Conductivity (Gallery) Cadmium reduction(Aquakem)

Cadmium reduction

pH and Conductivity

Cadmium reduction and automation

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Conclusions

• Determination of anions in wastewater is critical to verify its suitability for discharge

• Ion chromatography measures the conductivity of separated molecules while discrete analyzers use photometric assays that are specific for individual analytes

• Discrete analyzers • Automate photometric assays for fast, specific, high-throughput anionic

measurements of up to 600 tests/hour • Assays produce accurate, precise data even from challenging matrices

such as wastewater

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Thank You!